Cyanation of Unactivated Secondary Alkyl Halides

  • Author: ChemistryViews.org
  • Published: 18 November 2018
  • Copyright: Wiley-VCH Verlag GmbH & Co. KGaA
  • Source / Publisher: Organic Letters/ACS Publications
  • Associated Societies: American Chemical Society (ACS), USA
thumbnail image: Cyanation of Unactivated Secondary Alkyl Halides

Nitriles (pictured) are useful precursors for many types of compounds in organic synthesis. They can be prepared by nucleophilic substitution reactions of, e.g., alkyl halides with cyanide. However, the cyanide sources used for this are often very toxic. In addition, such substitution reactions at unactivated secondary alkyl halides can be challenging.


Yuanhong Liu and colleagues, Shanghai Institute of Organic Chemistry, University of the Chinese Academy of Sciences, have developed a nickel-catalyzed cyanation reaction of unactivated secondary alkyl chlorides or bromides which uses Zn(CN)2 as the cyanide source. Compared with standard reagents such as NaCN or KCN, Zn(CN)2 has a lower toxicity. The team used a variety of alkyl chlorides and bromides as substrates, NiCl2ยท6H2O as the catalyst, Xantphos (4,5-bis(diphenylphosphino)-9,9-dimethylxanthene) as a ligand, DMAP (4-dimethylaminopyridine) and n-Bu4NCl as additives, and CH3CN as the solvent.


The reaction gives the desired alkyl nitriles in good to high yields. A range of functional groups is tolerated. The team proposes a radical reaction mechanism. According to the researchers, the developed reaction is the first thermally driven metal-catalyzed cyanation of unactivated alkyl halides.


 

Article Views: 983

Sign in Area

Please sign in below

Additional Sign In options

Please note that to comment on an article you must be registered and logged in.
Registration is for free, you may already be registered to receive, e.g., the newsletter. When you register on this website, please ensure you view our terms and conditions. All comments are subject to moderation.

Article Comments - To add a comment please sign in

Bookmark and Share

If you would like to reuse any content, in print or online, from ChemistryViews.org, please contact us first for permission. more


CONNECT:

ChemistryViews.org on Facebook

ChemistryViews.org on Twitter ChemistryViews.org on YouTube ChemistryViews.org on LinkedIn Sign up for our free newsletter


A product of ChemPubSoc Europe (16 European Chemical Societies)and Wiley-VCH